CN103172677A - Organic metal iridium complex luminescent material and synthetic method of material - Google Patents
Organic metal iridium complex luminescent material and synthetic method of material Download PDFInfo
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- CN103172677A CN103172677A CN2013100888545A CN201310088854A CN103172677A CN 103172677 A CN103172677 A CN 103172677A CN 2013100888545 A CN2013100888545 A CN 2013100888545A CN 201310088854 A CN201310088854 A CN 201310088854A CN 103172677 A CN103172677 A CN 103172677A
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Abstract
The invention discloses an organic metal iridium complex luminescent material and a synthetic method of the material. The synthetic method disclosed by the invention comprises the following steps of: mixing an organic complex with iridium chloride hydrate in nitrogen atmosphere, subsequently adding a mixed solvent of tetrahydrofuran and water, heating in the nitrogen atmosphere and cooling to the room temperature; separating the reaction mixture liquid to acquire a tetrahydrofuran organic layer, and drying to remove the tetrahydrofuran solvent so as to acquire a metal iridium dimer complex; completely dissolving the metal iridium dimer complex and acetyl acetone thallium in dichloromethane and stirring at the room temperature in the nitrogen atmosphere; then purifying the metal iridium dimer complex on a chromatography silica gel column or a self-manufactured thin layer silica gel chromatography plate to acquire the final product which is the organic metal iridium complex luminescent material. According to the invention, the mixed solvent of the tetrahydrofuran and the water is taken as a reaction solvent for synthesizing the organic metal iridium complex, so that the synthetic yield of the organic metal iridium complex can be significantly improved; and the reaction after-treatment is simplified, so that the after-treatment time is shortened and the energy resources are saved.
Description
Technical field
The present invention relates to the luminous organic material field, particularly a kind of organic metal iridium complex luminescent material and synthetic method thereof.
Background technology
Luminous organic material is a kind of organic compound that can be luminous under optical excitation or electric shooting conditions.All kinds of new displays and head light running voltage by this class material preparation are low, and luminosity is high, energy-conserving and environment-protective.Especially the organic metal iridium complex luminescent material because can utilize simultaneously the molecule singlet and triplet state luminous, thereby make luminous internal quantum efficiency can reach 100% in theory, be subject to paying close attention to more and more widely.But at present the organic metal iridium Complex synthesis but causes to the solvability of reaction intermediate metal iridium Dimer Complex is relatively poor that reaction yield is very low even reacts because of the mixed reaction solvent of traditional ethylene glycol ethyl ether and water.In addition, the mixed solvent of ethylene glycol ethyl ether and water belongs to high boiling solvent, and it thoroughly will be removed after reaction need to be in vacuum drying oven dry nearly 10 hours, has both expended the energy, also needs the long period.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of organic metal iridium complex luminescent material and synthetic method thereof, with tetrahydrofuran (THF) and the water mixed solvent reaction solvent as the synthesis of organometallic complex of iridium, can improve reaction yield, reduce finishing time, save energy.
In order to achieve the above object, the technical solution adopted in the present invention is:
A kind of organic metal iridium complex luminescent material,
Its chemical formula is: C
71H
69B
2IrN
2O
2, molecular structural formula is:
Or its chemical formula is: C
99H
93B
2IrN
2O
2Si
2, molecular structural formula is:
Or its chemical formula is: C
75H
73B
2IrN
2O
6S
2, molecular structural formula is:
The synthetic method of above-mentioned organic metal iridium complex luminescent material comprises the following steps:
The first step: with organic ligand and hydration iridous chloride according to amount of substance (2-3): 1 ratio drops in reaction vessel, under nitrogen atmosphere, adding in the described reaction vessel can be with the tetrahydrofuran (THF) of reactants dissolved and the mixed solvent of water again, in mixed solvent, the volume ratio of tetrahydrofuran (THF) and water is (2-5): 1, be heated to 100 ℃ to 110 ℃ in nitrogen atmosphere, stir and be chilled to room temperature after 12 hours; Described organic ligand comprises 2-phenylpyridine and derivative compound thereof, 2-phenyl isoquinolin quinoline and derivative compound thereof, 2-phenylquinoline and derivative compound thereof, 2-phenyl thiazole and derivative compound thereof, 2-phenyl benzothiazole and derivative compound thereof etc. contain the compound of C^N double coordination structure;
Second step: reaction mixture final in step 1 is transferred to separatory in separating funnel, obtaining the upper strata is the tetrahydrofuran (THF) organic layer, and with anhydrous magnesium sulfate, that the tetrahydrofuran (THF) organic layer is dry, remove tetrahydrofuran solvent with Rotary Evaporators, can obtain reaction intermediate---the metal iridium Dimer Complex;
The 3rd step: need not purified metal iridium Dimer Complex, directly be dissolved in metal iridium Dimer Complex and methyl ethyl diketone thallium in methylene dichloride fully, metal iridium Dimer Complex and methyl ethyl diketone thallium according to the amount of substance ratio are: (2-3): 1, and in nitrogen atmosphere, stirring at room is 12 hours;
The 4th step: obtain thick product with the reaction soln of step 3 gained is concentrated, then with its purifying on chromatographic silica gel post or self-control thin layer silica gel chromatosheet, obtaining the finished product is the organic metal iridium complex luminescent material.
Compared with prior art, the invention has the beneficial effects as follows that tetrahydrofuran (THF) compares with the mixed solvent of water with traditional ethylene glycol ethyl ether with the mixed solvent of water, solvability to middle product metal iridium Dimer Complex will be got well, and can improve reaction raw materials to the development of evil in febrile disease rate of intermediate product metal iridium Dimer Complex.In addition, in last handling process, by separatory can desolventizing in the water of the overwhelming majority, in solvent, lower boiling tetrahydrofuran (THF) can be removed fast and needn't use vacuum drying oven with Rotary Evaporators, finishing time can shorten within an hour.So, use the mixed solvent of tetrahydrofuran (THF) and water not only can significantly improve reaction yield during the synthesis of organometallic complex of iridium, and can simplify the post-reaction treatment process, save energy and time.
Description of drawings
Fig. 1 is the route map by the synthetic metal iridium complex Ir1 of the present invention.
Fig. 2 is the route map by the synthetic metal iridium complex Ir2 of the present invention.
Fig. 3 is the route map by the synthetic metal iridium complex Ir3 of the present invention.
Fig. 4 is the metal iridium complex Ir1, the Ir2 that synthesize by selected three embodiment of the present invention and the luminous spectrogram of Ir3.
Wherein: IrCl
3H
2O is the hydration iridous chloride, and L1, L2, L3 are three kinds of organic ligands, and M1, M2, M3 are corresponding intermediate product metal iridium Dimer Complex, and Ir1, Ir2, Ir3 are corresponding organo-metallic complex of iridium, THF/H
2O represents the mixed solvent of tetrahydrofuran (THF) and water, CH
2Cl
2Be methylene dichloride, r.t. represents room temperature, h representative hour, and wavelength is wavelength, PL intensity (a.u.) is luminous intensity.
Embodiment
The present invention is further described below in conjunction with accompanying drawing.
Embodiment one:
The organic metal iridium complex luminescent material of the present embodiment, chemical formula is
C
71H
69B
2IrN
2O
2, structural formula is
Metal iridium complex Ir1, with reference to accompanying drawing 1, its synthetic route comprises the following steps:
The first step: 0.30 gram organic ligand L1 and 0.10 gram hydration iridous chloride are dropped in reaction vessel, the mixed solvent that adds 30 milliliters of tetrahydrofuran (THF)s and water in nitrogen atmosphere, in mixed solvent, the volume ratio of tetrahydrofuran (THF) and water is 3:1, be heated to 100 ℃ to 110 ℃ in nitrogen atmosphere, stir and be chilled to room temperature after 12 hours;
Second step: reaction mixture final in step 1 is transferred to separatory in separating funnel, obtaining the upper strata is the tetrahydrofuran (THF) organic layer, and with anhydrous magnesium sulfate, that the tetrahydrofuran (THF) organic layer is dry, remove tetrahydrofuran solvent with Rotary Evaporators, can obtain reaction intermediate---metal iridium Dimer Complex M1;
The 3rd step: need not purified metal iridium Dimer Complex M1, directly be dissolved in metal iridium Dimer Complex M1 and methyl ethyl diketone thallium in methylene dichloride fully, metal iridium Dimer Complex and methyl ethyl diketone thallium according to the amount of substance ratio are: 2.4:1, and in nitrogen atmosphere, stirring at room is 12 hours;
The 4th step: reaction soln is concentrated obtain thick product, then with its purifying on self-control thin layer silica gel chromatosheet, finally obtain 0.20 gram red solid Ir1, productive rate is 56%.
Its nuclear-magnetism characterization data is:
1H?NMR(400MHz,CDCl
3):δ(ppm)=8.54(d,2H),8.41(d,2H),8.24(s,2H),7.85(d,2H),7.64(t,2H),7.41(m,4H),6.79(s,8H),6.71(d,2H),6.36(d,2H),5.22(s,1H),2.30(s,12H),2.01(s,24H),1.78(s,6H).
According to above-mentioned data, illustrate the present embodiment synthetic be Ir1.
Embodiment two:
The organic metal iridium complex luminescent material of the present embodiment, chemical formula is
C
99H
93B
2IrN
2O
2Si
2, structural formula is
Metal iridium complex Ir2, with reference to accompanying drawing 2, its synthetic route comprises the following steps:
The first step: 0.42 gram organic ligand L2 and 0.10 gram hydration iridous chloride are dropped in reaction vessel, the mixed solvent that adds 30 milliliters of tetrahydrofuran (THF)s and water in nitrogen atmosphere, in mixed solvent, the volume ratio of tetrahydrofuran (THF) and water is 3:1, be heated to 100 ℃ to 110 ℃ in nitrogen atmosphere, stir and be chilled to room temperature after 12 hours;
Second step: reaction mixture final in step 1 is transferred to separatory in separating funnel, obtaining the upper strata is the tetrahydrofuran (THF) organic layer, and with anhydrous magnesium sulfate, that the tetrahydrofuran (THF) organic layer is dry, remove tetrahydrofuran solvent with Rotary Evaporators, can obtain reaction intermediate---metal iridium Dimer Complex M2;
The 3rd step: need not purified metal iridium Dimer Complex M2, directly itself and methyl ethyl diketone thallium are dissolved in appropriate methylene dichloride, metal iridium Dimer Complex M2 and methyl ethyl diketone thallium according to the amount of substance ratio are: 2.2:1, and in nitrogen atmosphere, stirring at room is 12 hours;
The 4th step: reaction soln is concentrated obtain thick product, then with its purifying on self-control thin layer silica gel chromatosheet, finally obtain 0.18 gram red solid Ir2, productive rate is 35%.
Its nuclear-magnetism characterization data is:
1H?NMR(400MHz,CDCl
3):δ(ppm)=8.36(s,2H),7.56(d,2H),7.49(t,4H),7.32(m,18H),7.21(m,12H),6.90(d,2H),6.73(s,8H),6.63(s,2H),4.90(s,1H),2.27(s,12H),1.80(s,24H),1.25(s,6H).
According to above-mentioned data, illustrate the present embodiment synthetic be Ir2.
Embodiment three
The organic metal iridium complex luminescent material of the present embodiment, chemical formula is
C
75H
73B
2IrN
2O
6S
2, structural formula is
Metal iridium complex Ir3, with reference to accompanying drawing 3, its synthetic route comprises the following steps:
The first step: 0.45 gram organic ligand L3 and 0.11 gram hydration iridous chloride are dropped in reaction vessel, the mixed solvent that adds 30 milliliters of tetrahydrofuran (THF)s and water in nitrogen atmosphere, in mixed solvent, the volume ratio of tetrahydrofuran (THF) and water is 3:1, be heated to 100 ℃ to 110 ℃ in nitrogen atmosphere, stir and be chilled to room temperature after 12 hours;
Second step: reaction mixture final in step 1 is transferred to separatory in separating funnel, obtaining the upper strata is the tetrahydrofuran (THF) organic layer, and with anhydrous magnesium sulfate, that the tetrahydrofuran (THF) organic layer is dry, remove tetrahydrofuran solvent with Rotary Evaporators, can obtain reaction intermediate---metal iridium Dimer Complex M3;
The 3rd step: need not purified metal iridium Dimer Complex M3, directly itself and methyl ethyl diketone thallium are dissolved in appropriate methylene dichloride, metal iridium Dimer Complex M3 and methyl ethyl diketone thallium according to the amount of substance ratio are: 2.9:1, and in nitrogen atmosphere, stirring at room is 12 hours;
The 4th step: reaction soln is concentrated obtain thick product, then with its purifying on self-control thin layer silica gel chromatosheet, finally obtain 0.10 gram red solid Ir3, productive rate is 18%.
Its nuclear-magnetism characterization data is:
1H?NMR(400MHz,CDCl
3):δ(ppm)=8.44(s,2H),7.84(dd,4H),7.56(d,2H),7.47(d,2H),7.42(t,3H),7.27(m,6H),6.84(s,8H),6.66(s,2H),5.01(s,1H),2.31(s,12H),2.07(s,24H),1.29(s,6H).
According to above-mentioned data, illustrate the present embodiment synthetic be Ir3.
Below by reference to the accompanying drawings the specific embodiment of the present invention is described; but these explanations can not be understood to limit scope of the present invention; protection scope of the present invention is limited by the claims of enclosing, and any change on claim of the present invention basis is all protection scope of the present invention.
Claims (2)
1. organic metal iridium complex luminescent material is characterized in that:
Its chemical formula is: C
71H
69B
2IrN
2O
2, molecular structural formula is:
Or its chemical formula is: C
99H
93B
2IrN
2O
2Si
2, molecular structural formula is:
Or its chemical formula is: C
75H
73B
2IrN
2O
6S
2, molecular structural formula is:
2. the synthetic method of an organic metal iridium complex luminescent material is characterized in that with tetrahydrofuran (THF) and water mixed solvent comprising the following steps as the reaction solvent of synthesis of organometallic complex of iridium:
The first step: with organic ligand and hydration iridous chloride according to amount of substance (2-3): 1 ratio drops in reaction vessel, under nitrogen atmosphere, adding in the described reaction vessel can be with the tetrahydrofuran (THF) of reactants dissolved and the mixed solvent of water again, in mixed solvent, the volume ratio of tetrahydrofuran (THF) and water is (2-5): 1, be heated to 100 ℃ to 110 ℃ in nitrogen atmosphere, stir and be chilled to room temperature after 12 hours; Described organic ligand comprises 2-phenylpyridine and derivative compound thereof, 2-phenyl isoquinolin quinoline and derivative compound thereof, 2-phenylquinoline and derivative compound thereof, 2-phenyl thiazole and derivative compound thereof, 2-phenyl benzothiazole and derivative compound thereof etc. contain the compound of C^N double coordination structure;
Second step: reaction mixture final in step 1 is transferred to separatory in separating funnel, obtaining the upper strata is the tetrahydrofuran (THF) organic layer, and with anhydrous magnesium sulfate, that the tetrahydrofuran (THF) organic layer is dry, remove tetrahydrofuran solvent with Rotary Evaporators, can obtain reaction intermediate---the metal iridium Dimer Complex;
The 3rd step: need not purified metal iridium Dimer Complex, directly be dissolved in metal iridium Dimer Complex and methyl ethyl diketone thallium in methylene dichloride fully, metal iridium Dimer Complex and methyl ethyl diketone thallium according to the amount of substance ratio are: (2-3): 1, and in nitrogen atmosphere, stirring at room is 12 hours;
The 4th step: obtain thick product with the reaction soln of step 3 gained is concentrated, then with its purifying on chromatographic silica gel post or self-control thin layer silica gel chromatosheet, obtaining the finished product is the organic metal iridium complex luminescent material.
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Cited By (3)
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| CN104004509A (en) * | 2014-04-15 | 2014-08-27 | 西安交通大学 | Organo-boron group-containing phosphorescent organic electroluminescent material and preparation method thereof |
| CN105481905A (en) * | 2015-12-29 | 2016-04-13 | 西安交通大学 | Asymmetric organic metal iridium complex phosphorescent material and preparation method thereof |
| CN114957343A (en) * | 2022-07-21 | 2022-08-30 | 西安交通大学 | Near-infrared luminescent molecule based on aryl boron substituted isoquinoline group |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104004509A (en) * | 2014-04-15 | 2014-08-27 | 西安交通大学 | Organo-boron group-containing phosphorescent organic electroluminescent material and preparation method thereof |
| CN105481905A (en) * | 2015-12-29 | 2016-04-13 | 西安交通大学 | Asymmetric organic metal iridium complex phosphorescent material and preparation method thereof |
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| CN114957343B (en) * | 2022-07-21 | 2024-05-07 | 西安交通大学 | Near infrared luminescent molecule based on aryl boron substituted isoquinoline group |
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